Alicyclic compound and curable resin composition

ABSTRACT

Decane compound or decene compound shown in the formula [1] below                    
     wherein A 1  and A 2  are independently hydrogen or (meth)acryloyl group or 2-vinyloxyethyl group; and the dotted line is single bond or double bond with the proviso that A 1  and A 2  are not hydrogen at the same time; and curable resin composition containing said compound therein. 
     The compound are suitable as the photo-monomer for resist raw materials because of high clarity at short wavelength ultraviolet light, dry etching resistance, adhesive property for the substrate and high solubility in alkaline developing solution in addition to high sensitivity and greater resolution; as the monomer for optic raw materials and disk overcoat materials because of high clarity, low birefringence and low water absorption rate; and as the monomer for the coating raw materials such as EB curable coating raw materials because of high reactivity, high wear characteristics and water resistance.

This is the National Phase Application of PCT/JP99/04929, filed Sep. 10,1999.

TECHNICAL FIELD

The present invention relates to tricyclo[5.2.1.0^(2,6)]decane compoundor tricyclo[5.2.1.0^(2,6)]dece-3-ene compound shown in the formula [1]below and the curable resin composition containing said compounddescribed above

wherein A¹ and A² are independently hydrogen; or acryloyl group ormethacryloyl group shown in the formula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; and R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; or 2-vinyloxyethyl group shown in the formula[3] below

—CH₂CH₂OCH═CH₂  [3]

wherein the dotted line is a single bond or double bond with the provisothat A¹ and A² are not hydrogen at the same time.

The compound in the present invention relates to the monomer used in thefield of pattern style materials suitable for the lithography withactive light radiation such as ultraviolet rays, far ultraviolet rays,electron rays, ion beam and X-rays, and the curable resin compositioncontaining said monomer. Further, the compound in the present inventionrelates to the monomer raw materials agent, optical materials andadhesive agents by having reactive ehtylenic unsaturated groups withinthe molecule as well as the highly heat resistant tricyclodecanestructure, and the curable resin composition containing said monomer.

BACKGROUND ART

Up to now, the compound shown in the formula below is known as thecompound having more than one unsaturated groups in the molecule ofalicyclic compound or as the main component of monomer raw materials forthe overcoat agent composition for optical disk (JP Laid-Open Hei1-121370).

The resin composition for optical raw materials consisting of thecompound shown in the formula below as the main component of saidcomposition is also known (JP Laid-Open Hei 2-115205).

In addition, the inventor of the present invention had already filed thepatent application relating totricyclo[5.2.1.0^(2,6)]dece-3-ene-8,9-dicarboxylic acid diallyl(abbreviated as TDEA) shown in the formula below (JP Laid-Open Sho60-156683).

However, polyester using TDEA have shown low reactivity ofpolymerization of allyl group and therefore the satisfactory result wasnot obtained in using said resin composition for acrylic optical rawmaterials.

Copolymer having adamantylmethacrylate unit of alicyclic polymer as apolymer compound with the clarity at 193 nm wavelength and yet with dryetching resistance [Takechi, S. et al., Journal of Photopolymer Scienceand Technology, 5 (3):439-446 (1992); and JP Laid-Open Hei 5-265212],poly (norbornylmethacrylate) [Endo, M. et al., Proceedings of IEDM],CA14-18, San Francisco (1992)] or copolymer having poly(isobornylmethacrylate) unit [Wallraff, G. M. et al., Journal of VacuumScience and Technology, B11 (6):2783-2788 (1993)], and copolymer havingpoly (menthylmethacrylate) unit [JP Laid-Open Hei 8-82925] have beenproposed.

On the other hand, aromatic derivatives such as2,2-bis(4-(2-vinyloxy)ethoxy)phenyl)propane shown in the formula below

or aliphatic vinylether derivatives such as bis(2-vinyloxyethyl)ether,1,2-bis[(2-vinyloxy)ethoxy]ethane and the like are well known asvinylether derivatives heretofore [Chemistry of Materials, 6 (10):1854-1860 (1994)].

However, alicyclic derivatives having vinyloxyethyloxymethyl group at 8and 9 positions of tricyclo[5.2.1.0^(2,6)]dece-3-ene ortricyclo[5.2.1.0^(2,6)]decane were not known at all.

The existing art described above do not contain residues which canmanifest the difference in solubility before and after the lightexposure within the residue unit of alicyclic group (adamantyl,norbornyl, isobornyl or menthyl) which result in dry etching resistance,and therefore the use as the resin component for the resist by preparingcopolymer with co-monomer such as t-butylmethacrylate ortetrahydropyranylmethacrylate which can manifest the difference insolubility has been employed in the pertinent art heretofore. However,the patterning has been employed in the pertinent art heretofore.However, the patterning requires about 30-50% co-monomer content, and asa result, the effect of dry etching resistance due to alicyclic groupstructure was drastically reduced and their utility have beenquestionable.

The existing art heretofore in use do not have any polar site within themolecules and therefore adhesion to the silicon substrate is poor. Inaddition, sensitivity is low because of low solubility in alkalinedeveloping aqueous solution, and furthermore, there is a shortcoming ofdregs left in the developing solution in all likelihood.

DISCLOSURE OF INVENTION

The object of the present invention is to prepare the novel alicycliccompound suitable as photo-monomer for the resist raw materials byhaving high clarity at short wavelength ultraviolet light and byexcelling in dry etching resistance due to tricyclo ring structure, andby showing adhesion for the substrate and high solubility in alkalinedeveloping solution in addition to high sensitivity and greaterresolution, as monomer for optic raw materials and disk overcoatmaterials by having high clarity, low birefringence and low waterabsorption rate, and as monomer for the coating raw materials such as EBcurable coating by having high reactivity, high wear characteristics andwater resistance and to provide the curable resin composition containingsaid compound.

The present inventors made the utmost effort in solving the problemsdescribed above. The present invention have been completed after theselection of tricyclodecanyl group as an alicyclic group in order toobtain high clarity and high dry etching resistance and the introductionof hydroxymethyl group as a polar substituent in order to achieve goodadhesion for the substrate and high solubility in alkaline developingsolution in addition to high sensitivity and greater resolution.

Thus, the present invention relates to tricyclo[5.2.1.0^(2,6)]decanecompound or tricyclo[5.2.1.0^(2,6)]dece-3-ene compound shown in theformula [1] below

wherein A¹ and A² are independently hydrogen; or acryloyl group ormethacryloyl group shown in the formula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; and R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; or 2-vinyloxyethyl group shown in the formula[3] below

—CH₂CH₂OCH═CH₂  [3]

wherein the dotted line is single bond or double bond with the provisothat A¹ and A² are not hydrogen at the same time, and the curable resincomposition containing said compound therein.

C₁-C₄ alkyl group in the definition of R¹ is straight or branched alkylgroup such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,s-butyl, t-butyl and the like.

C₁-C₁₀ alkyl group in the definition of R² and R³ is also straight orbranched alkyl group such as 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, nonyl,decyl and the like in addition to groups described above.

Following compounds described below may be abbreviated as shown in theleft.

DOL: 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]dece-3-ene

DH-DOL: 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane

DH-DOLMA: acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decane

DH-DOLMM:8-methacryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decane

DH-DOLDA: 8,9-bis(acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane

DH-DOLDM: 8,9-bis(methacryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane

DOLMV: 8(or 9)-hydroxymethyl-9(or8)-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]dece-3-ene

DH-DOLMV:8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decane

DOLVE:8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]dece-3-ene

DH-DOLVE:8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]decane

HVE: 2-haloethylvinylether

VEC: 2-chloroethylvinylether

Alicyclic compounds shown in the formula [1] above of the presentinvention can be grouped into A)-D) below.

A)8-(meth)acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decanecompound, or9-(meth)acryloyloxymethyl-8-hydroxymethyltricyclo[5.2.1.0^(2,6)]dece-3-enecompound or8-(meth)acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]dece-3-enecompound shown in the formula [4a] or [4b] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and the dotted line is single bond or doublebond.

B) 8,9-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decanecompound or8,9-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]dece-3-enecompound shown in the formula [5] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and the dotted line is single bond or doublebond.

C)8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decane,or8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]dece-3-eneor9-hydroxymethyl-8-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]dece-3-eneshown in the formula [6a] or [6b] below

wherein the dotted line is single bond or double bond.

D) 8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]decane or8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]dece-3-eneshown in the formula [7] below

wherein the dotted line is single bond or double bond.

The method of preparation for (meth)acryl compounds shown in the formula[4a] and [4b], and [5] are described in (1)-(3) of the Reaction Scheme Ibelow.

wherein R¹, R², R³ and the dotted line are the same meaning as above; R⁴is hydrogen or C₁-C₁₀ alkyl; and X is halogen.

8,9-bis(hydroxymethyl)tricycto[5.2.1.0^(2,6)]dece-3ene (DOL) shown inthe formula [8] as a starting raw material can be obtained by the methoddisclosed in JP Laid-Open Hei 8-206741 as described below.

That is to say that8,9-bis(alkoxycarbonyl)tricyclo[5.2.1.0^(2,6)]dece-3-ene (TCDE) can beobtained from the reaction with dicyclopentadiene (DCPD), carbonmonoxide and alcohol compound under the existence of ferric chloridewith palladium catalyst. DOL can be further obtained by the reduction ofthis TCDE.

In addition, 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane(DH-DOL) can be obtained by the method disclosed in JP Laid-Open Hei7-206740 by the present inventors described below.

Namely, said compound can be obtained either by the method in whichdouble bond in TCDE is first reduced before the reduction of carbonylgroup or by the method in which carbonyl group in TCDE is first reducedand then double bond in DOL thus obtained is reduced.

Further, R¹ in (meth)acryl compound shown in the formula [9] or theformula [10] as an other starting raw material is hydrogen or C₁-C₄alkyl group, and preferably hydrogen or C₁-C₂ alkyl group. Moreover, R²,R³ and R⁴ are hydrogen or C₁-C₁₀ alkyl group, and preferably hydrogen orC₁-C₅ alkyl group. Alkyl group in these examples cited are the numbersof carbon atoms corresponding to the examples of alkyl group in theembodiments described above.

Concrete examples of these (meth)acryl compounds are such as acrylicacid, methacrylic acid, tiglic acid, 3,3-dimethylacrylic acid,2-methyl-2-pentanoic acid, 2-ethyl-2-hexanoic acid and 2-octanoic acidand the like, and C₁-C₁₀ acrylic acid ester compound thereof such asacrylic acid methyl, acrylic acid ethyl, methacrylic acid methyl,methacrylic acid ethyl, tiglic acid methyl, tiglic acid ethyl,3,3-dimethylacrylic acid methyl, 3,3-dimethylacrylic acid ethyl,2-methyl-2-pentanoic acid methyl, 2-methyl-2-pentanoic acid ethyl,2-ethyl-2-hexanoic acid methyl, 2-ethyl-2-hexanoic acid ethyl,2-octanoic acid methyl and 2-octanoic acid ethyl, and the like.

The reaction (1) and (2) in the Scheme I require catalyst, and as suchmineral acid such as sulfuric acid, hydrochloric acid and nitric acidcan be used, and especially sulfuric acid is preferred. In addition,organic acid such as benzenesulfonic acid, p-toluenesulfonic acid,methanesulfonic acid, ethanesulfonic acid and trifluoro acetic acid canbe used, and p-toluensulfonic acid is preferred.

The moreover, tangstic acid, molybdic acid, and their heteropolyacid canbe named as catalyst. Typical examples of heteropolyacid are H₃PW₁₂O₄₀,H₄SiW₁₂O₄₀, H₄TiW₁₂O₄₀, H₅CoW₁₂O₄₀, H₅FeW₁₂O₄₀, H₆P₂W₁₈O₆₂, H₇PW₁₁O₃₃,H₄TiMo₁₂O₄₀, H₃PMo₁₂O₄₀, H₇PMo₁₁O₃₉, H₆P₂Mo₁₈O₆₂, H₄PMoW₁₁O₄₀,H₄PVMo₁₁O₄₀, H₄SiMo₁₂O₄₀, H₅PV₂Mo₁₀O₄₀, H₃PMo6W₆O₄₀,H_(0.5)Cs_(2.5)PW₁₂O₄₀ and their corresponding hydrates. In addition,catalyst with carbon or silica as a carrier can benamed. H₃PW₁₂O₄₀,H₃PMo₁₂O₄₀ and their hydrates among these heteropolyacid are the mostpreferred.

Furthermore, cation exchange resin such as Amberlite IR120 (trade name)and H-type zeolite such as H-ZSM-5 can also be used.

Especially, fatty acid salts of the compound from the second group ofperiodic table represented by 3ZnO-2B₂O₃, cadmium acetate, zinc acetateand calcium acetate in addition to mineral acids, heteropolyacids,organic acids, cation exchange resin and H-type zeolite described abovecan be used as examples of catalyst for transesterification method.

The amount of these catalyst used can be 0.1-100% by weight based on DOLor DH-DOL, and economically speaking 1-20% by weight is preferable.

Over excess amount of acrylic acid compound or acrylic acid estercompound can be used in the reactions (1) and (2) in Scheme I, but theuse of solvent is normally more preferred as the reaction can be carriedout in solvent after decreasing the amount of allylalcohol used to neartheoretical value. The kinds of solvent used are for example halogenatedhydrocarbon such as 1,2-dichloroethane (EDC) or 1,1,1-trichloroethane,aromatic hydrocarbon such as benzene, toluene or xylene, and ether suchas 1,2-dimethoxyethaneether or diethyleneglycoldimethylether.

The amount of solvent used is 1-20 fold by weight, more preferably 1-6fold by weight based on DOL or DH-DOL. The reaction temperature can be50-200° C., more preferably 70-150° C. The reaction can be carried outunder the normal pressure or increased pressure. The reaction time maybe 1-50 hours, but it is practical to carry out the reaction in 2-12hours under the normal circumstance.

The method of preparation for the reaction (3) in Scheme I will bedescribed in the followings.

(Meth)acryl acid halide shown in the general formula [11] can beobtained by converting said (meth)acryl acid compound to acid halidewith halogenated thionyl. Halogen atoms shown as radical X can be F, Cl,Br and I, but the cheapest Cl is normally selected. Typical example ofsaid compounds are such as acryloylchloride, methacryloylchloride,tiglyloylchloride, 3,3-dimethylacryloylchloride,2-methyl-2-pentenoylchloride, 2-ethyl-2-hexanoylchloride and2-octyloylchloride. The amount used is preferably 2.0-2.5 equivalent toDOL or DH-DOL.

Bases such as branched alkylamine compound such as trimethylamine,triethylamine and tripropylamine, aromatic amine compound such aspyridine, aniline and N-methylaniline, cyclic alkylamine compound suchas 1,5-diazabicyclo[4,3,0]-5-nonane (DBN), 1,4-diazabicyclo[2,2,2]octane(DBO) and 1,8-diazabicyclo[5,4,0]undece-7-ene (DBU), and metal carbonatesuch as sodium carbonate, sodium hydrogen carbonate and potassiumcarbonate are indispensable in the method shown in the reaction formula(3) in Scheme I. The preferred base among them is triethylamine ortripropylamine. The amount used is preferably 2.0-2.5 equivalent (sameequivalent as acid chloride) to DOL or DH-DOL.

The preferred method for the reaction (3) in Scheme I is to use solvent.Typical example of solvent preferred are ether compound such astetrahydrofuran (THF), 1,2dimethoxyethane, dioxane and2-methoxyethylether, N,N-dimethylformamide (DMF), N,N-dimethylacetoamide(DMAc), N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone (DMI).Among them, cheaper 1,2dimethoxyethane or DMF are preferred. Thepreferred amount to be used is 1-10 fold by weight, and especially 2-5fold by weight based on DOL or DH-DOL.

The reaction temperature is preferably 0-100° C., and the mostpreferably 0-50° C. Water is added to hydrolyze acid chloride left afterthe reaction, solvent is distilled off, extracted with water insolublesolvent (ether system or ester system), and then purified bydistillation or column chromatography to obtain the desired compound.

In addition, tricyclo[5.2.1.0^(2,6)]decane compound ortricyclo[5.2.1.0^(2,6)]dece-3-ene compound where both A¹ and A² are2-vinyloxyethyl group or either A¹ or A² is 2-vinyloxyethyl while theother is hydrogen can be synthesized by the Reaction Scheme II describedbelow.

wherein X is halogen atom.

Namely, (1) 8(or 9)-hydroxymethyl-9(or8)-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]dece-3-ene (DOLMV)can be obtained by reacting8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]dece-3-ene (DOL) and2-haloethylvinylether (HVE) under the existence of bases.

(2)8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decane(DH-DOLMV) can be obtained by reacting8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane (DH-DOL) and HVEunder the existence of bases.

(3) 8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]dece-3-ene(DOLVE) can be obtained by reacting DOL and 2 mole fold of HVE under theexistence of bases.

(4) 8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]decane(DH-DOLVE) can be obtained by reacting DH-DOL and 2 mole fold of HVEunder the existence of bases.

(5) DOLVE can be obtained by reacting DOLMV and HVE under the existenceof bases. (6) DH-DOLVE can be obtained by reacting DH-DOLMV and HVEunder the existence of bases.

On this occasion, typical examples of 2-haloethylvinylether, an otherraw material in addition to DOL and DH-DOL, shown in the formula [12]below

XCH₂CH₂OCH═CH₂  [12]

wherein X is halogen atom, are 2-fluoroethylvinylether,2-chloroethylvinylether, 2-bromoethylvinylether and2-iodoethylvinylether, and 2-chloroethylvinylether is used from theeconomical stand point of view. The preferred amount to be used is 1-10mole fold, especially 2-5 mole fold, based on DOL or DH-DOL.

The existence of bases is indispensable for the reaction (1)-(6) inScheme II above. The kind of bases that can be used may be hydroxide orhydride of alkaline metal and alkaline earth metal. Concrete examplesare such as LiOH, NaOH, KOH, RbOH, CsOH, Mg (OH)₂, Ca (OH)₂, Sr (OH)₂,Ba (OH)₂, LiH, NaH, KH, MgH₂, CaH₂, SrH₂ and Ba (OH)₂. Especially, NaOH,KOH, Ca (OH)₂, Ba (OH)₂, NaH and KH are preferred. The amount to be usedis 1-10 mole fold, and especially 2-5 mole fold is preferred based onthe reaction substrate.

The use of organic solvent is also preferred for the reaction (1)-(6) inScheme II. The kind of organic solvent preferred are amide familysolvent such as N,N-dimethylformamide (DMF), N,N-dimethylacetoamide(DMAc) or N-methylpyrrolidone, sulfoxide family solvent such asdimethylsulfoxide (DMSO) or sulfolane, aliphatic hydrocarbon familysolvent such as hexane, heptane or cyclohexane, aromatic hydrocarbonfamily solvent such as toluene, xylene or ethylbenzene, ether familysolvent such as dioxane, tetrahydrofuran (THF), 1,2-dimethoxyethane(DME) or diethylglycoldimethylether and water, one or more than twokinds can be used in homogeneous system or two phase system. The amountto be used may be 1-20 fold by weight, and especially 2-5 fold by weightis economical based on the reaction substrate.

Furthermore, the use of phase transfer catalyst is also effective forthe reaction (1)-(6) in Scheme II. The use of phase transfer catalyst isproductive, for example when alkaline metal or alkaline earth metal isto be used in amide family solvent or when alkaline metal or alkalineearth metal is to be used in the two phase solvent system withhydrocarbon solvent and water. Examples of phase transfer catalyst aresuch as tetrabutylammonium chloride, tetrabutylammonium bromide,trimethylbenzylammonium chloride, triethylbenzylammonium chloride,tetramethylammnoium chloride, tetraethylammonium bromide,tetra-n-butylammonium hydrogensulfate, trimethylbenzylammonium hydroxidemethanol solution and tetra-n-butylammonium hydroxide solution.

The amount to be used is 0.1-20% by weight, and preferably 0.5-10% byweight based on the reaction substrate is appropriate.

The reaction temperature is usually 0-150° C., but the reactiontemperature of 40-120° C. is preferred so as to increase the yield ofthe desired compound. The reaction can be carried out under the normalpressure or increased pressure.

The reaction time varies depending upon the kind of bases, amount,reaction temperature and solvent among other factors, but it is normallycarried out in 1-50 hours and the condition in which it can be over in2-20 hours is preferred. The reaction can be carried out by the batchmethod or the continuous method.

The reaction can be followed by sampling the reaction solution andanalyzing on gas chromatography. The isolation of the product can bedone by adding water and isopropylether, ethyl acetate ormethylethylketone (MEK) among others, dehydrating and concentrating theorganic phase, and the residue can be purified by distilling and/orapplying column chromatography to obtain the final product.

Acryloyl group or methacryloyl group thus obtained in the presentinvention, or alicyclic compound having 2-vinyloxyethyl group can beused as a monomer component of curable resin. In this instance, themonomer of the present invention alone can be used, but the use incombination with other acrylic family monomer is generally the norm. Asthings are, polymerization is carried out with catalyst (polymerizationinitiator) and solvent if necessary.

The monomer which can be used in combination are, without limitation,for example trimethylpropanetriacrylate, 1,6-hexanedioldiacrylate,neopentylglycoldiacrylate, trimethylolpropanedipropoxytriacrylate,polyethyleneglycoldiacrylate, tetrahydrofurfurylacrylate,4•5,8bis(acryloyloxymethyl)tricyclodecane, oxyethylenic bisphenol Adiacrylate, (meth)acrylic acid of bisphenol A-type glycidylether,(meth)acrylate of phenol novolac-type polyepoxy compound,methyl(meth)acrylate, carboxytricyclodecanylmethyl(meth)acrylate,2-methyladamantyl(meth)acrylate, trimethylnorbornyl(meth)acrylate,hydroxymenthyl(meth)acrylate and hydroxypivalic acid neopentylglycol.

The amount to be used of monomer such as (meth)acrylate other than thosedescribed above is less than 80% by weight, and preferably less than 70%by weight based on the total amount of the composition including thecompound of the present invention. The performance such as the adhesionof curable product can not be met if the amount to be used exceeds over80% by weight.

The initiator is normally added into the compound of the presentinvention or the curable resin composition containing said compound inorder to accelerate the cure reaction. For example, radicalpolymerization initiator is used for cure reaction with heat energy.Typical examples of the radical polymerization initiator are withoutlimitation organic peroxide such as benzoylperoxide, acetylperoxide,di-t-butylperoxide, t-butylperoxylaurate, dicumylperoxide,α,α′-bis-t-butylperoxy-p-diisopropylbenzene,2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-di-t-butylperoxyhexene,t-butyl peroxybenzoate, n-butyl-4,4-bis-t-butylperoxyvalerate,p-menthanehydroperoxide and t-butylcumylperoxide, or azobis compoundsuch as 2,2′-azobis(isobutyinitril),2,2′-azobis(2,4,4-trimethylvaleronitril) and2,2′-azobis(2-cyclopropylpropionitril).

Light polymerization initiator is used for cure reaction with energyrays. Known light polymerization initiator can be used for this purposeand examples as such are, without limitation, benzoin,benzoinmethylether, benzoinethylether, benzoinisopropylether,benzoinbutylether, benzoinphenylether, 1-hydroxycyclohexylphenylketone,3-methylacetophenone, 2,2-dimethoxyacetophenone,2,2-dimethoxy-2-phenylacetophenone, 4-dialkylaminoacetophenone,2-phenylthioacetophenone, benzyl, benzyldimethylketal, benzoylbezoate,anthraquinone, 2-ethylanthraquinone, naphthoquinone,2,4-diisopropylthioxanthone, azobisisobutyronitril,2,2′-azobis-2,4-dimethylvaleronitril, benzoylperoxide,di-t-butylperoxide, diphenyldisulfide, tetramethylthiurammonosulfide,tetraethylthiuramdisulfide, benzophenone, pivaloinethylether,dibenzylsulfide, cinnamoylchloride, dimethyldiphenylenedisulfide anddibenzothiazoledisulfide.

Furthermore, triboronfluoride ether, titanic acid tetraisopropyl and thelike may also be used as a cation polymerization initiator.

The amount of these radical polymerization initiator, lightpolymerization initiator and cation polymerization initiator to be usedis more than 0.01% by weight but less than 5% by weight, and preferablymore than 0.05% by weight but less than 3% by weight based on thecompound of the present invention or the curable resin compositionhaving said compound thereof. The cure rate is not practical if it isless than 0.01% by weight. In addition, if it exceeds 5% by weight, thenanymore improvement effect for cure rate can be expected and the weight,then anymore improvement effect for cure rate can be expected and theperformance of the cured film decreases, so it is not preferred.

The sensitizer can be added so as to potentiate the effect of lightpolymerization initiator into the compound of the present inventionwhich initiates the cure reaction with energy rays or the curable resincomposition having said compound therein. The sensitizer can not byitself be activated with the irradiation of energy rays, but thecombination increases the effectiveness when used together with lightinitiator than light initiator alone. Typical examples are, withoutlimitation, such as triethylamine, triethyltetramine, n-butylamine,di-n-butylamine, tri-n-butylphosphine, allylthiourea,s-benzylisothiuranium-p-toluenesulfinate anddiethylaminoethylmethacrylate.

The amount of the sensitizer to be used is more than 0.01% by weight butless than 5% by weight, and preferably more than 0.05% by weight butless than 3% by weight based on the compound of the present invention orthe curable resin composition having said compound therein. If it isless than 0.01% by weight, cure rate is too slow to be practical. Inaddition, if it exceeds 5% by weight, then anymore improvement effect asthe sensitizer can be expected and the performance of the cured filmdecreases, so it is not preferred.

Examples of the solvent used for polymerization are cyclic ether groupsuch as tetrahydrofuran and dioxane, glycol ether group such asethyleneglycolmonomethylether, ethyleneglycolmonoethylether,diethyleneglycolmonomethylether, diethyleneglycolmonoethylether anddiethyleneglycoldimethylether, propyleneglycolalkylether acetate groupsuch as propyleneglycol (mono) methylether acetate andpropyleneglycolpropylether acetate, ketone group such asmethylethylketone, cyclohexanone and 4-hydroxy4-methyl-2-pentanone,ester group such as 2-hydroxypropinic acid ethyl,2-hydroxy-2-methylpropionic acid ethyl, 2-hydroxy-2-methylpropionic acidethyl, ethoxyethyl acetate, hydroxy acid ethyl,2-hydroxy-3-methylbutanoic acid methyl, 3-methoxypropionic acid methyl,3-methoxypropionic acid ethyl, 3-ethoxypropionic acid ethyl,3-ethoxypropionic acid methyl, ethyl acetate, butyl acetate, methyllactate and ethyl lactate, cellosolve ester group such as methylcellosolve acetate and ethyl cellosolve acetate, aromatic hydrocarbongroup such as benzene, toluen and xylene, and aprotic polar solvent suchas DMF under the normal circumstances 20-1000 parts by weight to thetotal 100 parts by weight of polymeric component.

In the present invention, components such as inorganic filler materials,leveling agents, colorant, for example, pigment or dye, anti-formingagent, adhesive property impartant, plasticizer, solvent and storagestabilizer can be added at need to the compound of the present inventionor the curable resin composition having said compound therein.

As for the compound of the present invention in which energy rays leadsto cure reaction or the curable resin composition having said compoundtherein, typical examples of active light in order for the cure reactionto be taken place with the irradiation over the compound or thecomposition are ultraviolet rays, electron rays or X-rays. Sun light,chemical lamp, low pressure mercury vapor lamp, high pressure mercuryvapor lamp, metal halide lamp or xenon lamp among others can be used asthe light source for ultraviolet rays.

The field of application for the curable resin composition having saidalicyclic compound of the present invention are such as adhesive, paint,ink, building material, lighting, glass fiber reinforced resin, rust andcorrosion prevention, optical lens, optical fiber coating, UV•EB curableresin and resist.

Especially, the alicyclic compound of the present invention excels asphotosensitive monomer suitable for resist raw material because of highclarity at short wavelength ultraviolet rays, high dry etchingresistance due to tricyclic ring structure and strong adhesive propertyagainst silicone substrate, as the optic raw material and the diskovercoat raw material because of high clarity, low birefringence and lowwater absorption rate, and as the suitable coating raw material such asUV•EB curable coating material because of high reactivity, high wearcharacteristics and water resistance.

Furthermore, the compound of the present invention can also be used asthe dental restoration raw material. They excel in for example adhesiveproperty against dentin and blocking property for the vicinity of dentinand restoration material. In addition, the dental adhesive having mono(meth)acrylate compound with hydroxy group within the molecule of thepresent acrylate compound with hydroxy group within the molecule of thepresent invention have good balance for adhesive property, blockingproperty and hydrophilic nature among others.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described further in more details by showingthe examples, but the invention is not limited to the particularembodiments described herein.

EXAMPLE 1

3.92 g (20 mmol) of DH-DOL, 40 ml of tetrahydrofuran (THF) and 2.02 g(20 mmol) of triethylamine were charged into a 100 ml 4-mouthed reactionflask and cooled to 5° C. Under stirring, the mixed solution of 1.82 g(20 mmol) of acryloylchloride and 10 ml of THF was added drop-wise. Thereaction solution was stirred for one hour at 5° C. and then furtherreacted for 6 hours at 25° C. The reaction solution was filtered and thefiltrate was concentrated. The residue was dissolved in chloroform,washed with 0.5 N-hydrochloric acid solution, saturated salt solution,3% sodium carbonate solution and saturated salt solution in succession,and concentrated under the reduced pressure after dehydration withanhydrous magnesium sulfate. The concentrated residue was purifiedthrough the silica gel column chromatography with n-hexane/ethylacetate=4/1 to yield 1.14 g (Yield 23%) of8-acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decane(DH-DOLMA) and 1.25 g (Yield 21%) of8,9-bis(acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane (DH-DOLDA) wereobtained.

The structure of DH-DOLMA was confirmed with the analytical resultsdescribed below.

MASS (FAB⁺, m/e (%)): 251 (M⁺1, 16), 220 (25), 179 (27), 177 (47), 161(92), 133 (35), 119 (44), 101 (67), 94 (100), 84 (63), 71 (40). ¹H-NMR(CDCl₃, δ ppm): 1.37 (dt, J₁=10.25 Hz, J₂=1.47 Hz, 1H), 1.48-1.69 (m,7H), 2.06 (d, J=12.0 Hz, 2H), 2.12 (d, J=7.7 Hz, 1H), 2.15 (s, 1H), 2.24(dd, J₁=15.29 Hz, J₂=8.33 Hz, 1H), 2.44 (d, J=2.56 Hz, 2H), 3.49 (dd,J₁=10.62 Hz, J₂=7.69 Hz, 1H), 3.69 (dd, J₁=10.53 Hz, J₂=6.68 Hz, 1H),4.06 (dd, J₁=11.08 Hz, J₂=8.33 Hz, 1H), 4.25 (dd, J₁=10.99 Hz, J₂=6.59Hz, 1H), 5.83 (dd, J₁=8.61 Hz, J₂=1.47 Hz, 1H), 6.12 (dd, J₁=17.30 Hz,J₂=10.34 Hz, 1H), 6.40 (dd, J₁=17.39 Hz, J₂=1.47, 1H). ¹³C-NMR (CDCl₃, δppm): 26.78 (2), 29.01, 37.11, 38.31, 40.71 (2), 44.68, 45.02, 45.53,45.59, 62.92, 65.16, 128.50, 130.8, 166.29. IR (KBr, cm⁻¹): 3420, 2950,1720,1410, 1300, 1200, 1050, 1020, 980, 810.

EXAMPLE 2

7.84 g (40 mmol) of DH-DOL, 3.24 g (45 mmol) of acrylic acid, 0.23 g ofp-toluene sulfonic acid monohydrate, 0.20 g of hydroquinone and 20 ml ofbenzene were charged into a 100 ml 4-mouthed reaction flask, the mixturewas stirred for 4 hours while the product water was distilled off withthe concomitant increase in the temperature from 90-104° C. The mixturewas cooled after the completion of the reaction and then1,2-dichloroethane (EDC) and water were added, and EDC layer was washedwith saturated salt solution, 5% sodium hydrogen carbonate solution andagain saturated salt solution in succession. This EDC layer wasconcentrated under reduced pressure and the residue was purified throughthe silica gel column chromatography to yield 2.08 g (Yield 21%) ofDH-DOLMA of the object.

EXAMPLE 3

3.92 g (20 mmol) of DH-DOL, 30 g of THF and 2.02 g (20 mmol) oftriethylamine were charged into a 100 ml 4-mouthed reaction flask andcooled to 5° C. The mixed solution of 2.09 g (20 mmol) ofmethacryloylchloride and 10 g of THF was drop-wise added into thereaction mixture with stirring. Stirring was continued for one hour at5° C. and then the mixture was additionally reacted for 6 hours at 25°C. The mixture was concentrated under reduced pressure at 25° C. andthen 1,2-dichloroethane (EDC) and water were added to the residue andEDC layer was separated. This EDC layer was washed with0.5%-hydrochloric acid solution, saturated salt solution, 3% sodiumhydrogen carbonate solution, and again saturated salt solution insuccession, and the layer was dried with anhydrous sodium sulfate andconcentrated under reduced pressure. This concentrated residue waspurified through the silica gel column chromatography withn-hexane/ethyl acetate=4/1 to yield 1.48 g (Yield 28%) of8-methacryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decane(DH-DOLMM) and 1.39 g (Yeld 21%) of8.9-bis(methacryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane (DH-DOLDM).

The structure of DH-DOLMM was confirmed with the analytical resultsdescribed below.

MASS (FD⁺, m/e (%)):265 (M⁺1, 55), 178 (100). ¹H-NMR (CDCl₃, δ ppm):1.27 (s, 2H), 1.48-1.68 (m, 9H), 1.95 (s, 3H), 2.07 (d, J=15.5 Hz, 2H),2.45 (s, 2H), 3.48 (dd, J₁=8.05 Hz, J₂=10.25 Hz, 1H), 3.68 (dd, J₁=6.77Hz, J₂=10.44 Hz, 1H), 4.04 (dd, J₁=8.51 Hz, J₂=10.89 Hz, 1H), 4.24 (dd,J₁=6.23 Hz, J₂=10.99 Hz, 1H), 5.56 (dd, J₁=1.47 Hz, J₂=3.11 Hz, 1H),6.09 (s, 1H), ¹³C=NMR (CDCl₃, δ ppm): 14.13, 18.30, 22.71, 26.82, 29.04,31.90, 37.13, 38.26, 40.67, 44.69, 45.62, 62.7, 65.24, 125.45, 136.38,167.50.

EXAMPLE 4

7.84 g (40 mmol) of DH-DOL, 3.87 g (45 mmol) of methacrylic acid, 0.23 gof p-toluene sulfonic acid monohydrate, 0.20 g of hydroxyquinone and 20ml of benzene were charged into a 100 ml 4-mouthed reaction flask, andthe mixture was stirred for 4 hours while the product water wasdistilled off with the concomitant increase in the temperature from90-106° C. The mixture was cooled after the completion of the reactionand then 1,2-dichloroethane (EDC) and water were added, and EDC layerwas washed with saturated salt solution, 5% sodium hydrogen carbonatesolution and again saturated salt solution in succession. After this EDClayer was concentrated under reduced pressure, the residue was purifiedthrough the silica gel column chromatography to yield 1.19 g (Yield 18%)of DH-DOLMM of the object.

EXAMPLE 5

422 g (2.15 mole) of DH-DOL was dissolved into 6 L of tetrahydrofuran(THF), and 438 g (4.84 mole) of acryloylchloride was added. 480 g (4.84mole) of triethylamine was drop-wise added into the mixture over 30minutes after cooled to 0° C. After the completion of drop-wiseaddition, the reaction was completed two hours after gradually raisingthe temperature to room temperature (25° C.). The mixture wasconcentrated under reduced pressure after the addition of 3 L of waterand THF was distilled off. The pH of water layer was adjusted to pH 8with triethylamine and then extracted with diisopropylether thrice. Theextracted solution were combined and concentrated under reducedpressure, and then the residue was purified through the silica gelcolumn (SiO₂: 3 Kg×2, eluate: n-hexane/ethyl acetate=10/1). 510 g (Yield77.9%) of oily product was obtained at the room temperature as the mainfraction. Incidentally, this oily product became solidified after keptin −40° C. refrigerator over night and then returned to the roomtemperature. The analytical results of this crystal were as follows.

Melting point (° C): 33-34; MASS (FD⁺, m/e (%)): 304 (M⁺, 100), 160(45). ¹H=NMR (CDCl₃, δ ppm): 1.41 (d, J=10.3 Hz, 2H), 2.08 (s, 2H),2.26-2.29 (m, 2H), 2.46 (s, 2H), 4.06-4.10 (m, 2H), 4.20 (dd, J₁=5.86Hz, J₂=11.0 Hz, 2H), 5.83 (dd, J₁=1.47 Hz, J₂=10.4 Hz, 2H), 6.13 (c,J₁=10.4 Hz, J₂=17.2 Hz, 2H), 6.41 (dd, J₁=1.47 Hz, J₂=1.72 Hz, 2H).

From the results described above, the product was confirmed as8.9-bis(acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane.

EXAMPLE 6

7.84 g (40 mmol) of DH-DOL, 6.48 g (90 mmol) of acrylic acid, 0.23 g ofp-toluene sulfonic acid, 0.20 g of hydroxyquinone and 4 ml of benzenewere mixed and stirred with the removal of water while raising thetemperature to 90-106° C. After the reaction was completed, the mixturewas concentrated under the reduced pressure after the addition of 1.4 mlof water. The mixture was extracted with the addition of 20 ml ofdiisopropylether and then washed with 5% NaCl solution, 2% NaOH solutionand further 5% NaCl solution. After the concentration under reducedpressure, the residue was purified through the silica gel to yield 3.5 g(Yield 28.7%) of 8,9-bis(acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decaneof the object.

EXAMPLE 7

340 g (1.73 mole) of DH-DOL was dissolved into 5.1 L of tetrahydrofuran(THF) and then 526 g (5.19 mole) of triethylamine was added. 408 g (5.19mole) of methacryloyloxychloride was drop-wise added to this mixtureafter the mixture was cooled to 0° C. After the completion of drop-wiseaddition, the mixture was continuously stirred for three hours whilegradually raising the temperature to room temperature (25° C.) tocomplete the reaction. Then, the mixture was concentrated under thereduced pressure after the addition of water, and THF was distilled off.Isopropylether (IPE) was added to the residue and the product wasextracted.

This IPE solution was concentrated under the reduced pressure to yield550 g of white crystal. This impure crystal was re-crystallized withn-hexane/ethyl acetate=20/1 to yield 110.3 g of white crystal with 99.1%purity with liquid chromatography. The filtrate was further purifiedthrough the silica gel column (SiO₂: 5 Kg) after concentration to yield206.6 g of white crystal with 99.3% purity with liquid chromatography.The same product was obtained after re-crystallization. The results aredescribed below.

Melting point (° C): 72-73; MASS (FD⁺, m/e (%)): 332 (M⁺, 100), 279(35). ¹H-NMR (CDCl₃, δ ppm): 1.41 (d, J=10.3 Hz, 1H), 1.41 (d, J=10.3Hz, 1H), 1.52-1.56 (m, 6H), 1.70 (d, J=10.3 Hz, 1H), 1.95 (s, 6H), 2.09(s, 2H), 2.27 (t, J=3.9 Hz, 2H), 2.46 (s, 2H), 4.04-4.09 (m, 2H),4.19-4.22 (m, 2H), 5.56 (s, 2H), 6.11 (s, 2H).

From the results described above, the product was confirmed as8,9-bis(methacryloyloxymnethyl)tricyclo[5.2.1.0^(2,6)]decane.

EXAMPLE 8

20 g (102 mmol) of 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane(DH-DOL), 13.47 g (204 mmol) of 85% potassium hydroxide and 90 ml ofDMSO were charged into a 300 ml 4-mouthed reaction flask and heated to60° C. Next, 43.47 g (408 mmol) of 2chloroethylvinylether (VEC) wasdrop-wise added at 70° C. The mixture was then stirred for three hoursat 75-80° C. 6.74 g (102 mmol) of 85% potassium hydroxide and 21.74 g(204 mmol) of VEC were further added. The mixture was stirred foranother one hour with heating and the reaction mixture was tested on thethin chromatography, and only the product was identified concomitantwith the disappearance of raw materials.

Next, water and ethyl acetate were added to the reaction mixture, andthe organic layer was washed with water, dehydrated with anhydrousmagnesium sulfate and concentrated under the reduced pressure. Theconcentrated residue was purified through the silica gel columnchromatography with n-hexane/ethyl acetate=6/1-2/1 to yield 27.8 g(Yield 100%) of oily product (later solidified upon storage at 5° C.).The analytical results of this product were as follows.

Melting point (° C): 33-34; MASS (FD⁺, m/e (%)): 266 (M⁺, 100), 249(18), 194 (13). ¹H-NMR (CDCl₃, δ ppm): 1.32 (d, J=8.4 Hz, 1H), 1.49 (d,J=9.8 Hz, 3H), 1.55-1.64 (m, 4H), 1.88 (d, J=12.4 Hz, 2H), 2.17 (s, 1H),2.31 (s, 1H), 2.39 (s, 2H), 3.40-3.45 (m, 2H), 3.64-3.75 (m, 5H), 3.83(t, J=4.0 Hz, 2H), 4.01-4.04 (m, 1H), 4.16-4.20 (m, 1H), 6.47-6.52 (m,1H). ¹³C-NMR (CDCl₃, δ ppm): 26.71, 26.76, 29.00, 38.09, 39.68, 41.66,45.62, 45.72, 45.85, 45.94, 64.04, 66.79, 69.30, 73.52, 86.85, 151.56.

From the results described above, the product was confirmed as8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decane.

EXAMPLE 9

1.96 g (10 mmol) of DH-DOL and 20 ml of DMF were charged into a 50 ml4-mouthed reaction flask and 1 g (25 mmol) of 60% NaH was added withstirring in an ice bath. The temperature of the mixture was thengradually raised to room temperature to 50° C. and stirred for twohours. 2.67 g (25 mmol) of VEC was drop-wise added after the mixture wasagain cooled to 0° C. The temperature was adjusted to room temperatureagain and the then reaction was carried out for three hours. Water andethyl acetate were added to the reaction mixture, and then the organiclayer was washed with water and concentrated, and the concentratedresidue was purified through the silica gel column chromatography toisolate 1.14 g (Yield 42.9%) of DH-DOLMV and 0.71 g (Recovery 36.2%) ofDH-DOL, the raw material.

EXAMPLE 10

3.92 g (20 mmol) of DH-DOL and 60 ml of DMF were charged into a 100 ml4-mouthed reaction flask and 4.8 g (120 mmol) of 60% NaH was added withstirring in an ice bath over 30 minutes. The temperature was graduallyraised to room temperature to 100° C. and stirred for 18 hours. 8.53 g(80 mmol) of VEC was drop-wise added after the mixture was cooled againto 0° C. The temperature of the mixture was adjusted to room temperatureagain and the reaction was carried out for three hours. Water and ethylacetate were added, and the organic layer was washed with water andconcentrated, and the concentrated residue was purified through thesilica gel column chromatography to isolate 3.68 g (Yield 69.1%) ofDH-DOLMV and 0.82 g (Recovery 21.0%) of DH-DOLO, the raw material.

EXAMPLE 11

1.96 g (10 mmol) of DH-DOL, 10 ml of toluene, 3.96 g (60 mmol) of 85%KOH, 10 ml of water and 1.29 g (4 mmol) of tetrabutylammonium bromidewere charged into a 50 ml 4-mouthed reaction flask and 4.26 g (40mmol)of VEC was drop-wise added with stirring. After the temperature wasraised to 70° C. and the reaction was carried out for 67 hours, 2.13 g(20 mmol) of VEC was further added and reacted for 24 hours. After themixture was cooled and separated with the addition of water, the waterlayer was extracted with ethyl acetate, the combined organic layer waswashed with water, then dehydrated with anhydrous magnesium sulfate andconcentrated under the reduced pressure. The concentrated residue waspurified through the silica gel column chromatography withn-hexane/ethyl acetate=6/1-2/1 to yield 1.85 g (Yield 70%) of DH-DOLMVand 1.07 g (Yield 28%) of a new component. The analytical results forthis new oily product are as described below.

MASS (FD⁺, m/e (%)): 336 (M⁺, 100), 269 (28), 249 (19), 195 (23). ¹H-NMR(CDCl₃, δ ppm): 1.30 (d, J=9.9 Hz, 1H), 1.48 (d, J=9.0 Hz, 1H), 1.59(dd, J₁=12.8 Hz, J₂=10.3 Hz, 6H), 2.05 (s, 2H), 2.16 (d, J=11.5 Hz, 2H),2.40 (s, 2H), 3.33 (dd, J₁=1.5 Hz, J₂=7.6 Hz, 2H), 3.51-3.54 (m, 2H),3.59-3.66 (m, 4H), 3.79-3.83 (m, 4H), 3.99-4.01 (m, 2H), 4.18 (dd,J₁=12.2 Hz, J₂=2.1 Hz, 2H), 6.50 (dd, J₁=7.47 Hz, J₂=5.87 Hz, 2H).¹³C-NMR (CDCl₃, δ ppm): 26.78, 29.06, 37.83, 38.56, 44.98, 45.73, 67.44,69.13, 71.96, 76.82, 86.61, 151.89.

From the results obtained above, the product was confirmed as8,9-bis[(2-vinyloxoethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]decane(DH-DOLVE).

EXAMPLE 12

145 g (0.74 mmol) of DH-DOL, 40 ml of toluene, 95.4 g (0.3 mmol) oftetrabutyl ammonium bromide, 293 g (4.44 mmol) of 85% KOH and 740 ml ofwater were charged into a 2 L 4-mouthed reaction flask and 315.5 g (2.96mmol) of VEC was drop-wise added with stirring at room temperature. Thetemperature was raised to 70° C. and continuously stirred for 95 hours.After the further addition of 139.5 g (1.31 mmol) of VEC, the reactionwas carried out for 28 hours. Water was added after cooling, toluenelayer was separated, the water layer was extracted with ethyl acetateand mixed with toluene layer, and then dehydrated with anhydrousmagnesium sulfate to yield the oily product upon concentration. Afterthe addition of 0.5 g of hydroquinone to this oily product andimpurities with low boiling point were removed by distillation under thereduced pressure (oil bath 106-135° C./1.6 mm Hg), and the residue waspurified through the silica gel column chromatography withn-hexane/ethyl acetate=6/1-2/1. The obtained impure DH-DOLVE and impureDH-DOLMV were each dissolved into acetone, decolored with activatedcharcoal (5% addition), filtered and then distilled off acetone to yield41 g (Yield 16%) of DH-DOLVE and 123 g (Yield 63%) of DH-DOLMV(stabilizer: addtion of about 100 ppm of hydroquinone monomethylether).

EXAMPLE 13

1.96 g (10 mmol) of DH-DOL, 3.5 ml of DMSO and 1.32 g (20 mmol) of 85%KOH were charged into a 50 ml 4-mouthed reaction flask and stirred forone hour at 60° C. After the drop-wise addition of 4.26 g (40 mmol) ofVEC at 70° C., the mixture was stirred for three hours at 75-80° C. 0.32g (1 mmol) of tetrabutyl ammoniumbromide, 0.66 g (10 mmol) of 85% KOHand 2.13 g (20 mmol) of VEC were further added and the mixture wasstirred for one hour with heating. Although DH-DOL, the raw material,disappeared, 0.66 g (10 mmol) of 85% KOH and 2.13 g (20 mmol) of VECwere further added and stirred for 5 hours with heating. Water and ethylacetate were added after cooling, the organic layer was washed withwater, dehydrated with anhydrous magnesium sulfate, and concentrated.The concentrated residue was purified through the silica gel columnchromatography to yield 0.58 g (Yield 17%) DH-DOLVE and 1.89 g (Yield71%) of DH-DOLMV.

EXAMPLE 14

2.66 g (10 mmol) of DH-DOLMV, 10 ml of toluene, 0.32 g (1 mmol) oftetrabutyl ammoniumbromide and 0.8 g (20 mmol) of NaOH dissolved in 5 mlwater were charged into a 50 ml 4-mouthed reaction flask and the mixturewas stirred for one hour at 60° C. Next, 4.26 g (40 mmol) of VEC wasdrop-wise added at 70° C. The temperature of the mixture was raised to75-80° C. and stirred for three hours. After the further addition of 2.0g (50 mmol) of NaOH, 4.26 g (40 mmol) of VEC was added and stirred forthree hours. After the reaction was completed, toluene layer wasseparated and combined with the extract of water layer with ethylacetate, dehydrated with anhydrous magnesium sulfate to yield the oilyproduct upon concentration. The oily product was purified through thesilica gel column chromatography to yield 1.25 g (Yield 37%) of DH-DOLVEwith 95.8% purity with gas chromatography.

EXAMPLE 15

2.66 g (10 mmol) of DH-DOLMV obtained in Example 12, 10 ml of DMSO and1.32 g (20 mmol) of 85% KOH were charged into a 50 ml 4-mouthed reactionflask and stirred for one hour at 60° C. After the further addition of4.26 g (40 mmol) of VEC drop-wise at 70° C., the mixture was stirred forthree hours at 75-80° C. After the addition of 1.32 g (20 mmol) of 85%KOH, additional 4.26 g (40 mmol) of VEC was added and stirredcontinuously for three hours. Water and ethyl acetate were added afterthe reaction solution was cooled to room temperature, and the organiclayer was dehydrated with anhydrous magnesium sulfate, thenconcentrated, and the residue was purified through the silica gel columnchromatography to yield 0.98 g (Yield 29%) of DH-DOLVE.

EXAMPLE 16

(DG-DOLDA photo-setting and characteristics)

A sample with following composition was prepared and used for theevaluation. 5 parts by weight of 1-hydroxycyclohexylphenylketone(produced by Ciba Speciality Chemicals Co., Irgcure-184®) as a lightpolymerization initiator was added to the composition comprising of 45parts by weight of8,9-bis(acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decane (DH-DOLDA)obtained in Example 5, 20 parts by weight oftrimethyrolpropanedipropoxytriacrylate (produced by Nihon Kayaku K.K.,TPA-320®), 30 parts by weight of hydroxypivalic acid neopentylglycol(produced by Nihon Kaykaku K.K., KAYARAD-MANDA®) and 5 parts by weightof tetrahydrofurfurylacrylate (produced by Osak Yuki Co., THFA®). Theobtained mixture was applied over the glass substrate by spincoating andthen light-cured with a high-pressure mercury lamp until the completeloss of tack. Following characteristics were examined for the obtainedcoating.

1) Clarity; the transmission at 400 nm through the film with 3 μm inthickness on the quart substrate after curing was 98%. The haze was lessthan 0.1% and transparent.

2) Refractive index; 1.5097 (633 nm), birefringence 0.0000

3) Pencil hardness; HB

4) Water absorption rate; 0.62%

5) Heat resistance; 10% weight reduction temperature; 241° C.

6) Electrical characteristics; dielectric constant 3.25 (1 KHz),dielectric dissipation factor 0.0342 (1 KHz), volume resistance 5×10 15Ωcm

7) Adhesive property; cellophane tape peeling test was conducted after across cut was made on the bare silicon substrate, but peeling was notobserved.

EXAMPLE 17

(Synthesis of DH-DOLMV homo-polymer)

Under nitrogen gas atmosphere, 2 g of8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decane(DH-DOLMV) was dissolved to 10% by weight in diglyme(diethyleneglycoldimethylether). Three drops of borontrifluorideethersolution as a cation polymerization initiator was added with a pipetteinto this solution and cation polymerization was conducted at 70° C. for24 hours with heating and constant stirring. The molecular weightdistribution of the obtained polymer with gel filtration chromatography(polystyrene conversion) was confirmed and number-average molecularweight (Mn) was 8543, weight-average molecular weight (Mw) was 27337,and the ratio of Mw/Mn was 3.2.

EXAMPLE 18

(Synthesis of DH-DOLMA and acrylic acid methyl copolymer)

Under nitrogen gas atmosphere, 2.5 g of8-acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decane(DH-DOLMA) and 2.5 g of acrylic acid methyl were dissolved in 20 g ofcyclohexanone. 0.1 g of 2,2′-azobis(isobutylonitrile) was added into thesolution as a polymerization initiator and radical polymerization wasconducted at 70° C. for 24 hours with heating and constant stirring. Themolecular weight distribution of the obtained polymer with gelfiltration chromatography (polystyrene conversion) was confirmed and Mnwas 7841, Mw was 29012, and the ratio of Mw/Mn was 3.7. Monomer topolymer conversion rate was followed with gas chromatography, but theconversion rate remains nearly the same and random copolymer wasobtained.

EXAMPLE 19

(Synthesis of DH-DOLMA homo-polymer and their property)

Under nitrogen gas atmosphere, 2 g of8-acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decan(DH-DOLMA) was dissolved into 20 g of the solution consisting of2-heptanone and propyleneglycol monomethylether acetate with 1:1 weightratio. 0.16 g of 2,2′-azobis(isobutylonitrile) was added into thesolution as a radical polymerization initiator and radicalpolymerization was conducted at 70° C. for 24 hours with heating andconstant stirring. The molecular weight distribution of the obtainedpolymer with gel filtration chromatography (polystyrene conversion) wasconfirmed and Mn was 2434, Mw was 5841, and the ratio of Mw/Mn was 2.4.Special properties as described below were investigated for the obtainedpolymer.

1) Refractive index; 1.536 (633 nm)

2) Water absorption rate; 0.61%

3) Heat resistance; 10% weight reduction temperature; 251° C.

4) Glass transition temperature; not detected up to 150° C. withdifferential scanning calorimetric measurement

5) Adhesive property; cellophane tape peeling test was conducted after across cut was made on the bare silicon substrate, but peeling was notobserved.

INDUSTRIAL APPLICABILITY

Alicyclic compound of the present invention is industrially usefulcompound as a monomer for curable resin and the curable resincomposition having said compound therein are suitable as resist rawmaterials because of dry etching resistance and the improvement inadhesive property, as optical raw materials and disk overcoat rawmaterials because of the improvement in clarity, low birefringence andlow rate of water absorption and also as coating raw materials such asUV•EB cure coating because of reactivity, wear resistance and waterresistance.

What is claimed is:
 1. Tricyclo[5.2.1.0^(2,6)]decane compound ortricyclo[5.2.1.0^(2,6)]dece-3-ene compound shown in the formula [1]below

wherein A¹ and A² are independently hydrogen; or acryloyl ormethacryloyl shown in the formula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; and R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; or 2-vinyloxyethyl group shown in the formula[3] below —CH₂CH₂OCH═CH₂  [3] wherein the dofted line is single bond ordouble bond with the proviso that A¹ and A² are not hydrogen at the sametime. 2.8-(meth)acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0^(2,6)]decanecompound or 9(or 8)-(meth)acryloyloxymethyl-8(or9)-hydroxymethyltricyclo[5.2.1.0^(2,6)]dece-3-ene compound according toclaim 1, where A¹ in the formula [1] is acryloyl group ormethacryloylgroup as shown in the formula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and A² is hydrogen as shown in the formula[4a] or [4b] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and the dotted line is single bond or doublebond.
 3. 8,9-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0^(2,6)]decanecompound or8,9-bis((meth)acryoyloxymethyl)tricyclo[5.2.1.0^(2,6)]dece-3-enecompound according to claim 1, where A¹ and A² are the same or differentin the formula [1], and acryoyl group or methacryloyl group shown in theformula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and shown in the formula [5] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; and the dotted line is single bond or doublebond. 4.8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]decaneor 8(or 9)-hydroxymethyl-9(or8)-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0^(2,6)]dece-3-eneaccording to claim 1, where A¹ in the formula [1] is 2-vinyloxyethylgroup shown in the formula [3] below —CH₂CH₂OCH═CH₂  [3] and A² ishydrogen, as shown in the formula [6a] or [6b] below

wherein the dotted line is single bond or double bond. 5.8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]decane or8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0^(2,6)]dece-3-eneaccording to claim 1, where A¹ and A² in the formula [1] are2-vinyloxyethyl group shown in the formula [3] below —CH₂CH₂OCH═CH₂  [3]as shown in the formula [7] below

wherein the dotted line is single bond or double bond.
 6. Curable resincomposition containing tricyclo[5.2.1.0^(2,6)]decane compound ortricyclo[5.2.1.0^(2,6)]dece-3-ene compound shown in the formula [1]below

wherein A¹ and A² are independently hydrogen; or acryloyl group ormethacryloyl group shown in the formula [2] below

wherein R¹ is hydrogen or C₁-C₄ alkyl; R² and R³ are independentlyhydrogen or C₁-C₁₀ alkyl; or 2-vinyloxyethyl group shown in the formula[3] below —CH₂CH₂OCH═CH₂  [3] wherein the dotted line is single bond ordouble bond with the proviso that A¹ and A² are not hydrogen at the sametime.